Methods and compositions for removing sulfur from liquid hydrocarbons

Abstract

Improved desulfurization compositions are provided for removing substantial fractions of sulfur, sulfur complexes, and sulfur compounds from liquid hydrocarbons such as crude oil and fuels. The preferred compositions comprise respective quantities of an alkylphenol ethoxylate, an amine, and an alkali metal nitrite. The compositions may be contacted with liquid hydrocarbons to achieve high levels of desulfurization.

1 . A composition comprising respective quantities of an alkylphenol ethoxylate and a nitrite.  
     
     
         2 . The composition of  claim 1 , said alkylphenol ethoxylate having a C4-C12 straight or branched chain alkyl group therein.  
     
     
         3 . The composition of  claim 2 , said alkylphenol ethoxylate being nonylphenol ethoxylate having from about 4-120 ethoxylate moieties therein.  
     
     
         4 . The composition of  claim 1 , said composition further including an amine selected from the group consisting of primary, secondary, tertiary and quaternary mono- and polyamines and mixtures thereof.  
     
     
         5 . The composition of  claim 4 , said amine selected from the group consisting of compounds of the formula (R1) 2 —N—R2—R3) 2 , where R2 is selected from the group consisting of aryl, alkyl, cycloalkyl, arylalkyl, alkoxyalkyl and hydroxyalkyl groups, and mixtures thereof, R3 is selected from the group consisting of H and N(R1) 2  groups and mixtures thereof, where each R1 is independently selected from the group consisting of H, aryl, alkyl, cycloalkyl, arylalkyl, alkoxyalkyl and hydroxyalkyl groups, and mixtures thereof.  
     
     
         6 . The composition of  claim 5 , said amine comprising a fatty acid diamine.  
     
     
         7 . The composition of  claim 6 , said fatty acid diamine being a C8-C24 fatty acid diamine.  
     
     
         8 . The composition of  claim 1 , said nitrite is selected from the group consisting of the alkali metal nitrites.  
     
     
         9 . The composition of  claim 1 , said composition including an amine, said alkylphenol ethoxylate being present at a level of from about 0.5-65% by weight, said amine being present at a level of from about 0.5-50% by weight, and said alkali metal nitrite being present at a level from about 0.5-70% by weight.  
     
     
         10 . The composition of  claim 9 , said alkylphenol ethoxylate being present at a level of from about 30-50% by weight, said amine being present at a level of from about 5-20% by weight, and said alkali metal nitrite being present at a level from about 40-60% by weight.  
     
     
         11 . The composition of  claim 10 , said alkylphenol ethoxylate being present at a level of about 40% by weight, said amine being present at a level of about 10% by weight, and said alkali metal nitrite being present at a level of about 50% by weight.  
     
     
         12 . A method of reducing the content of sulfur and/or sulfur-bearing compounds in a liquid hydrocarbon comprising the step of contacting the liquid hydrocarbon with an effective amount of a composition comprising respective quantities of an alkylphenol ethoxylate and a nitrite.  
     
     
         13 . The method of  claim 12 , said alkylphenol ethoxylate having a C4-C12 straight or branched chain alkyl group therein.  
     
     
         14 . The method of  claim 13 , said alkylphenol ethoxylate being nonylphenol ethoxylate having from about 4-120 ethoxylate moieties therein.  
     
     
         15 . The method of  claim 12 , said composition including an amine selected from the group consisting of primary, secondary, tertiary and quaternary mono- and polyamines and mixtures thereof.  
     
     
         16 . The method of  claim 15 , said amine selected from the group consisting of compounds of the formula (R1) 2 —N—R2—(R3) 2 , where R2 is selected from the group consisting of aryl, alkyl, cycloalkyl, arylalkyl, alkoxyalkyl and hydroxyalkyl groups, and mixtures thereof, R3 is selected from the group consisting of H and N(R1) 2  groups and mixtures thereof, where each R1 is independently selected from the group consisting of H, aryl, alkyl, cycloalkyl, arylalkyl, alkoxyalkyl and hydroxyalkyl groups, and mixtures thereof.  
     
     
         17 . The method of  claim 16 , said amine comprising a fatty acid diamine.  
     
     
         18 . The method of  claim 17 , said fatty acid diamine being a C8-C24 fatty acid diamine.  
     
     
         19 . The method of  claim 12 , said nitrite selected from the group consisting of the alkali metal nitrites.  
     
     
         20 . The method of  claim 12 , said alkylphenol ethoxylate being present at a level of from about 0.5-65% by weight, said amine being present at a level of from about 0.5-50% by weight, and said alkali metal nitrite being present at a level from about 0.5-70% by weight.  
     
     
         21 . The method of  claim 20 , said alkylphenol ethoxylate being present at a level of from about 30-50% by weight, said amine being present at a level of from about 5-20% by weight, and said alkali metal nitrite being present at a level from about 40-60% by weight.  
     
     
         22 . The method of  claim 21 , said alkylphenol ethoxylate being present at a level of about 40% by weight, said amine being present at a level of about 10% by weight, and said alkali metal nitrite being present at a level of about 50% by weight.  
     
     
         23 . The method of  claim 12 , said liquid hydrocarbon selected from the group consisting of crude oil and fuels derived from crude oil.  
     
     
         24 . The method of  claim 12 , said composition being in solid form.  
     
     
         25 . The method of  claim 12 , said composition being in the form of an aqueous dispersion.  
     
     
         26 . The method of  claim 25 , said aqueous dispersion comprising from about 1-1.5 lbs. of said composition per gallon of aqueous liquid.  
     
     
         27 . The method of  claim 12 , said composition being contacted with said liquid hydrocarbon at a level of from about 250-20,000 ppm of the composition per ppm of total sulfur in the liquid hydrocarbon.  
     
     
         28 . The composition of  claim 1 , said ethoxylate and nitrite being separate.  
     
     
         29 . The method of  claim 12 , said contacting step comprising the step of individually contacting said liquid hydrocarbon with said ethoxylate and nitrite.